TW211020B - Dithiocarbamate polymers - Google Patents

Abstract

A water soluble ethylene dichloride ammonia polymer having a molecular weight of from 500 to 10,000 which contains from 5 to 50 mole % of dithiocarbamate salt groups. Also, disclosed are the use of these polymers in removing heavy metals from water.

Description

2110-, 0 A6 B6 Central Bureau of Economic Development, Ministry of Economic Affairs, Angong Consumer Cooperatives, Yinfan 5 'Description of the invention () This invention is the treatment of blue wastewater. More particularly, the present invention is a periodical water-soluble dioxocarbamate polymer and its method of use in a gold removal process. As rivers, waterways, etc. are more and more caused by industrial wastewater pollution, more and more vigorous regulations have been formulated to avoid this pollution. Today, it is a mandatory requirement to control the Jinyong in wastewater below its legal concentration. Among them, special regulations have been established for heavy metals harmful to humans, such as mercury, cadmium, zinc, copper and chromium. Multiple methods have been proposed to use M to remove heavy metals from wastewater. In one method, a simple dithiocarbamate (such as dimethyldiaminocarbamate, DMDTC) is used to achieve heavy gold removal. The use of low molecular weight dithiocarbamic acid has several disadvantages. The precipitate formed may be a small one, and it may be slow to settle the sediment from the waste water or filter it out. Therefore, in order to obtain faster sinking and filtering, it is often necessary to add additional flocculants and / or accelerators. To improve the ability of dithioamine formate to remove gold ions, it is reacted with polyethylenimine polymer. This proposal is contained in European Patent Application 0009551 A1. The polyethylenimine polymer described in this patent is water-insoluble. Although it has been shown to have the ability to inhibit mal-competitive gold hurricanes, the separation of chelated metal / polymer complexes is quite slow. The function of this type of material is similar to that of water-insoluble ion exchange resins. Another example of polyethylenimine-dithiocarbamate polymer is contained in U.S. Patent No. 4,670,160. In Example 8 of the patent, (please read the precautions on the back before writing this page) 丨 Install · Order · This paper size is applicable to China National Standard (CNS) Grade 4 (210 X 297 public loan) 3 81.9 .25,000 A6 B6 Printed by the R & C Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs. 5. Description of the invention () It is mentioned that the polyethylenimine resin with a molecular weight of 60,000 is modified with M disulfide. Although the completed resin proved to be somewhat water-soluble, it still contained substantial amounts of insoluble materials. The experimental data indicates that although the polyethylenimine resin can be modified with M2S to produce a water-soluble resin, its molecular weight must be about 10,000 or less. In addition, the available amount of disulfide is 25 mol% or less. The purpose of the present invention is to propose a polymer-type dithiocarbamate polymer which is water-soluble and has poor integration of heavy metals making it easy Ability to be removed from the water system. According to this, the present invention proposes a water-soluble dichloroethylene / ammonia polymer, which is characterized in that it has a molecular weight of 500 to 100,000 and contains 5 to 50 mole percent of dithiocarbamate groups. The present invention also proposes a method for removing some gold tallow from water containing heavy metals * which is characterized by the following steps E: a) Water solubility with a mismatch amount, a molecular weight of 500 to 100,000 and containing 5 to 50 mole percent Dithiocarbamate-based two-gas ethylene / ammonia polymer treats this type of water to form complexes of these heavy metals; b) allows these complexes to quickly settle into precipitates from water; and c). The precipitate was separated in water. Vinyl chloride-ammonia polymer This polymer is made by the reaction of vinyl chloride and ammonia. The typical reactions of such polymers will be described later. The starting two-gas ethylene-ammonia polymer usually has a molecular weight range of 500-100,000. In a preferred embodiment, the numerator is set to 1,500 to 10,000, and its most appropriate (please read the precautions on the back and then fill out this page) i Packed · The size of the paper is applicable to China National Standard (CNS) A 4 Specifications (210 X 297 mm) 4 81.9.25,000 21i ❶ Lv) A6 B6 5. Description of the invention () The molecular weight range is 1,500-5,000. In order to illustrate the preparation of the seed polymer, the following Example 1 is proposed. Trial Example 1 In a pressure reactor, 10.8% of the weight of water-containing ammonia, 7.7% by weight of anhydrous ammonia, 2.3% by weight of water and 0.3% by weight of EDT A were fed. Seal the reactor and heat to 115-1301 :, then pump in ethylene dichloride (EDC). After adding about 0.5% by weight of £ 0 (: After that, add 50% sodium hydroxide at the same rate as EDC and complete the addition within 4.5 hours. During the addition of the reactants, take samples of them. Then these The sample was concentrated under reduced pressure to remove residual EDC, NH3 and reaction by-product-gaseous ethylene. After that, the weight average molecular weight of the polymer was measured by the phase analysis and polyethylene glycol standard. A series of polymers was prepared , Its composition and properties are listed in Table 1. (Please read the precautions on the back and fill in this page) Order · Printed by the Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperatives 1 搛 S # wtXRnn Wt.XNanH \ hL ttn .Polymerization and dispersion of the same polymer 1 12.9 10.4 1380 1010 1.3 41.2 2 15.4 12.3 1620 1100 1.5 46.4 3 17.5 15.2 1670 1100 1.5 41.9 4 20.2 19.3 1850 1290 1.6 43.1 5 22.3 23.1 2320 1290 1.8 37.8 6 24.7 25.7 2970 1440 2.0 47.1 7 26.7 27.4 3470 1540 2.2 41.5 8 29.2 29.2 4420 1700 2.6 42.5 9 32.1 32.8 6040 1910 3.1 37.9 10 33.8 34.6 7970 1910 4.2 36.5 11 36.3 42.6 92,100 2600 35.0 35.0 National Standards (CNS) A4 specifications (210 X 297 mm) 5 81.9.25,000 2ll〇r- ° A6 B6 Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ V. Description of invention () Polymerization with disulfide The reaction of modified polyamines or polyimines with dinitrated nitric acid to produce dithiocarbamate or its salts is well known. This reaction, described elsewhere, is described in US Patent 4,731,187 The patent is therefore listed as a reference for the present invention. The reaction between polyamine and diamine is more appropriate in a solvent such as water or alcohol. The reaction is within the range of 30-100t: temperature It can be carried out smoothly for a period of 1 to 10 hours. Good conversion can be achieved at a temperature of 40-70 ° C for 2 to 5 hours. These general reaction conditions can be modified with M2 to improve the second gas ethylene-ammonia polymer mentioned above. The mol% of the dithiocarbamate group contained in the finished polymer is usually in the range of 5 to 50 mol%. The more suitable range is 20-40 mol%, and the most suitable range is about 25 -35 mol%. For conversion of vinyl chloride polymer to dithiocarbamate group The reaction is to propose Example 2 described below. Jian Yuli P. Add 38 grams of 50% sodium hydroxide and 41 grams of deionized water to 82 grams of EDC / NH3 polymer. The resulting mixture was placed in a pressure reactor and 14 grams of sulfur disulfide was added. Then, the mixture was heated to 45-50 ° C for three hours. After a reaction time of three hours, the mixture was cooled and vacuum was applied for five minutes to remove residual disulfide. The resulting solution product contains 30% modified polymer. Using this split preparation technology, the following modified polymers were prepared: (see Table 2) ---------------- ^ Youi (please also read the notes on the back and fill in this Page) i Pack · Order-This paper scale is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 public goods) 6 81.9.25,000 Α6 Β6 V. Description of the invention (Table 2 Examined by MJ. Mil K 会 物 an 50! KNanH Detailed counterproduct f A 2970 22.1 8.0 21 21.7 soluble B 2970 20.9 9.7 26 20.5 soluble C 2970 18.0 11.1 35 22.3 soluble D 3470 20.6 9.6 26 20.2 soluble E 3420 18.9 11.7 35 18.5 soluble F 4400 20.1 9.4 26 25.0 Insoluble G 4092 22.0 8.0 21 17.1 Insoluble H 4096 22.0 8.0 10 17.1 Soluble I 1850 20.6 4.0 21 21.1 Soluble (please read the precautions on the back before filling this page) Central Ministry of Economic Affairs 8 Printing and Printing by the Consumer Cooperative Co., Ltd. with the increase of the molecular weight of the cistern "can be used to react to form a water-soluble reaction product. The amount of disulfide is decreasing. When the CSa content in the polymer is less than about 20 mol, the metal removal efficiency It will be reduced. The dose can effectively remove Jin Yun's hair from contaminated water The amount of modified polymer is usually in the range of 0.5 to 3 gram of polymer per gram of heavy metal contained in the water to be treated. Generally speaking, 1 to 1.5 grams of heavy gold per mol of water Excellent results can be obtained with molecular polymers. The dosage can be expressed in another form. 3-10 ml of 0.3% polymer active solution per gram of molecular water can produce a surprising metal removal effect. And make the formed complex into self-flocculation, that is, it can be quickly settled and easily separated from the treated water. This paper scale is applicable to China Solid National Standard (CNS) A 4 specifications (210 X 297 mm) -1-81.9.25,000

V. Description of the invention () Example 3 In order to illustrate the ability of the urethane polymers listed in Table 2 to effectively remove and retreat from the supply water, the phase data is presented in Table 3. Table 3 Hafnium polluted water, indium (oDn), party material, taki (fag) / 100 · 丨 Sleep water polymer 0 6 9 12 15 18 A 20 — 1.1 0.09 0.05 1 B 20 3.9 0.2 0.07 0.07 0.05 C 20 3.1 0.2 0.06 0.05 0.05 D 20 3.4 0.1 0.06 0.04 0.04 E 20 2.2 0.11 4.06 0.06 0.06 Η 20 one 0.14 0.08 0.08 — < please first hear the $ 面 之 注 $ item and then I)-丨 Installation- Order The quasi-room R-consumer cooperation du printing must mention in particular that the observed filtration rate is fast. Advantages of the invention 1. The EDC / HH3 polymer can be derivatized under csa under mild conditions to form a water-soluble polymerized dithioamine formate polymer. 2. The polymer-type lithium dithiocarbamate can chelate and precipitate heavy metals from wastewater faster than DMDTC (small molecules), as evidenced by the rapid formation of precipitates. 3. In addition to its good chelating ability, the polymerized dithiocarbamate also has a larger precipitate than the one produced by DMDTC and settles very quickly. Because of the large sediments, there is no need to add accelerators or flocculation. The first line · clothing paper / L degree is applicable to the Chinese standard (CNS> A 4 specifications (210 X 297 g *)) 82.3. 40.000 g \ 1〇 一ο Fifth, the description of the invention () agent to help deposition. Therefore, the polymer-type dithiocarbamate of the present invention can be a single-step treatment type chemical that uses M to remove heavy gold from the wastewater. (Please read the precautions on the back before writing this book)-Binding · Order · Printed by the Staff Consumption Cooperative of the Central Standards Bureau of the Ministry of Economy and Economy. The size of the paper is in accordance with China National Standard (CNS) Grade 4 (210 X 297 mm) 9 81.9.25,000

Claims (1)

6. Patent application Fan Yuan 1. A water-soluble dichloroethylene-ammonia polymer, which is characterized in that it has a molecular weight of 500 to 100, 000 and contains 5 to 50 mole percent of diamine amine formate group . 2. The water-soluble dichloroethylene-ammonia polymer of item i in the scope of patent application is characterized in that its molecular weight is 1500 to 10,000 and it contains 15 to 50 mole percent of diaminoamine formate groups. 3. The water-soluble dichloroethylene-ammonia polymer as claimed in item 1 of the patent application is characterized in that its molecular weight is 1500 to 5000 and it contains approximately 25 to 40 mole percent of dithiocarbamate. 4. A method for removing these gold ions from heavy metal-containing water, the particular advice is to include the following steps: a) Use a mismatched amount of 500 to 100,000 and contain 5 to 50 mole percent of dithiocarbamate The water-soluble difluoroethylene-ammonia polymer treats the water M to form complexes of these heavy metals; b) allows the complex to rapidly precipitate from the water into a precipitate; and c) separates the precipitate from the water . 5. The method as claimed in item 4 of the patent application is characterized in that the water-soluble polymer has a molecular weight of 1500 to 10,000 and it contains 15 to 50 mole percent of dithiocarbamate groups. 6. As in the method of claim 4 of the patent application, wherein the water-soluble polymer has a molecular weight of 1500 to 5000 and contains about 25 to 40 mole percent of dibenzylamine formate groups. (Please read the precautions on the back before filling in this page) • Order · Line · Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs f 4 (210X297 Public Broadcasting) 10 78. 8. 3,000